EP0192356A2 - Polyacetal resin composition - Google Patents

Polyacetal resin composition Download PDF

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Publication number
EP0192356A2
EP0192356A2 EP86300552A EP86300552A EP0192356A2 EP 0192356 A2 EP0192356 A2 EP 0192356A2 EP 86300552 A EP86300552 A EP 86300552A EP 86300552 A EP86300552 A EP 86300552A EP 0192356 A2 EP0192356 A2 EP 0192356A2
Authority
EP
European Patent Office
Prior art keywords
resin composition
polyacetal resin
stage
polyacetal
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP86300552A
Other languages
German (de)
French (fr)
Other versions
EP0192356A3 (en
Inventor
Yukio Ikenaga
Masami Yamawaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polyplastics Co Ltd
Original Assignee
Polyplastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co Ltd filed Critical Polyplastics Co Ltd
Publication of EP0192356A2 publication Critical patent/EP0192356A2/en
Publication of EP0192356A3 publication Critical patent/EP0192356A3/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C08L59/02—Polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • This invention relates to a polyacetal resin composition suitable for use in the field of metallized articles.
  • Polyacetals have many excellent characteristics, such as mechanical, anti-static, thermal, long-term, and molding properties. They are therefore, widely utilized as engineering plastics for functional components in various industrial fields, such as machine parts and electrical components. In such areas as automotive vehicle parts, where impact resistance is required, polyacetal resins are used effectively, and in order to give an appealing appearance to such parts, it is a current practice to metallize the polyacetal resin. In this connection, there has hitherto been much research into metallizing techniques and other areas.
  • metallizing of a polyacetal resin results in a lowering of its impact resistance, which is an otherwise advantageous characteristic feature of the resin.
  • metallizing has been considered undesirable.
  • many automotive vehicle parts for which any deterioration in impact performance due to metallizing is disfavoured There are, for example, many automotive vehicle parts for which any deterioration in impact performance due to metallizing is disfavoured.
  • one object of the present invention is the provision of metallized products having excellent impact properties.
  • a metallized product having excellent impact properties by using, for a product which is to be metallized, a polyacetal resin composition incorporating a specific polyacrylate resin.
  • a polyacetal resin composition of the invention. comprises 50 to 99.5 percent by weight of polyacetal and 0.5 to 50 percent by weight of a two or more stage polyacrylate comprising a rubber-like first stage and a thermoplastic rigid final stage.
  • the polyacrylate is preferred to be a two-stage polymer which has been obtained by polymerizing monomers such as. butyl acrylate, butylene diacrylate and allyl methacrylate or di-allyl maleate in the first stage and polymerizing methyl methacrylate in the final stage.
  • one aspect of the invention provides a polyacetal composition comprising 0.5 to 50 percent by weight of a particular polyacrylate-resin based modifier incorporated into a polyacetal, and more specifically, a polyacetal resin composition wherein the polyacetal resin contains 0 to 10 percent by weight of an inorganic substance, or more particularly calcium carbonate.
  • the modifier composed of a particular polyacrylate resin is advantageously a multi-stage polymer having a rubber-like first stage and a thermoplastic rigid final stage. One or more intermediate stages may be selected.
  • an intermediate stage may be a polymerization of about 75 to 100 percent by weight of styrene.
  • a particularly preferred polyacrylate-based modifier consists of a two-stage polymer, the first stage being a polymerization of monomers including a butyl acrylate and a butylene diacrylate as a crosslinking agent, and allyl methacrylate or diallyl maleate as a grafting agent.
  • Acryloid KM330 a product of Rohm & Haas (U.S. Pat. No. 4,096,202) can be used in the composition of the present invention.
  • the modifier composed of such polyacrylate resin is added in a proportion of 0.5 to 50 percent by weight relative to the entire amount of the composition. If the addition is less than 0.5 percent by weight, there is no noticable improvement in the impact property, and if the addition is more than 50 percent by weight, it may be unfavourably reflected in the physical properties of the molded product. Preferably, the addition should be within the range of 3 to 15 percent by weight. If the plate adhesion of the metallized article is considered, an optimum range of addition is 5 to 15 percent by weight.
  • a polyacetal used in the composition of this invention may be a homopolymer or a copolymer. There is no particular limitation in respect of polymerization degree; the polyacetal is acceptable if it has a fair molding fluidity and if it has suitable mechanical properties for the intended product.
  • the resin may contain other components such as a lubricant and a stabilizer.
  • a polyacetal resin containing an inorganic substance is preferable to use.
  • useful inorganic substances are calcium carbonate, glass, silica, talc, and pumice: more particularly, calcium carbonate is preferred.
  • Such polyacetal resin presents a moderately rough surface after it has been subjected to pre-metallizing surface treatment, that is to say, etching, and has high activity; therefore, it exhibits very high plate adhesion.
  • pre-metallizing surface treatment that is to say, etching
  • the effect of calcium carbonate on plate adhesion is satisfactory where the addition is 1 to 10 percent by weight relative to the composition as a whole: and good surface luster effect is also obtainable in that case. If the addition is more than 10 percent by weight, no stable plate adhesion can be obtained, nor is it possible to obtain a good surface effect.
  • Addition of an inorganic substance also contributes towards improving the rigidity of molded products and reducing possible dimensional change.
  • the inorganic substance has a particle diameter, in the range of between tens of millimicrometres (mum) and say ten odd micrometres ( ⁇ m); in the case of calcium carbonate, for example, heavy calcium carbonate. coke, and light calcium having a particle diameter of tens of micrometres ( ⁇ m).
  • various synthetics of the type having a particle diameter ranging from ten millimicrometres (m ⁇ m) to hundreds of millimicrometres (mpm). may be considered.
  • coarse particles one micrometre ( ⁇ m) to ten odd micrometres ( ⁇ m)
  • fine-particle calcium carbonate is preferred, rather than heavy calcium carbonate.
  • composition of this invention can be prepared in various ways. For example, the resin component and the modifier are melted and kneaded and then extruded into pellets by means of an extruder, which pellets are then turned out into moldings by using a molding machine.
  • the composition of the invention can be satisfactorily metallized according to any known method.
  • Metallizing can be performed with a good plate adhesion effect by passing through such stages as degreasing, acid etching, washing, sensitizing, activation, or a combination of sensitizing and activation, such as, catalyst treatment, electroless plating, and electroplating.
  • etching by acid is carried out by dipping in a mixed solution of hydrochloric acid and sulfuric acid, for example. a mixed solution containing concentrated hydrochloric acid, concentrated sulfuric acid, and water in the ration of 1 : 1 : 2 by volume (about 8.6 wt % HCl + about 35.3 wt % H 2 SO 4 ) for 5 to 30 minutes.
  • a polyacrylate-based modifier consisting of a multi-stage polymer having a rubber-like first stage and a thermoplastic rigid final stage (Acryloid KM330, a product of Rohm & Haas) and calcium carbonate in such ratio as shown in Table 1.
  • the mixture was melted, kneaded, and extruded into a molding by an extruder: the molding was annealed and degreased, and then subjected to etching: subsequently, the stock was subjected to catalyst treatment and finally to metallizing.
  • the metallized product thus obtained was tested for measurement as to Izod impact strength (notched). Also, a scar 1 cm in length, extending from the plated surface to the resin layer was given to the metallized product by using a knife, and the load required in peeling off the plate was measured for evaluation of the plate adhesion.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

A polyacetal resin composition comprises polyacetal and a two- or more-stage polyacrylate comprising a rubber-like first stage and a thermoplastic rigid final stage. It is useful for an impact resistant metallized article.

Description

  • This invention relates to a polyacetal resin composition suitable for use in the field of metallized articles.
  • Polyacetals have many excellent characteristics, such as mechanical, anti-static, thermal, long-term, and molding properties. They are therefore, widely utilized as engineering plastics for functional components in various industrial fields, such as machine parts and electrical components. In such areas as automotive vehicle parts, where impact resistance is required, polyacetal resins are used effectively, and in order to give an appealing appearance to such parts, it is a current practice to metallize the polyacetal resin. In this connection, there has hitherto been much research into metallizing techniques and other areas.
  • Generally, however, metallizing of a polyacetal resin results in a lowering of its impact resistance, which is an otherwise advantageous characteristic feature of the resin. For some products, therefore, metallizing has been considered undesirable. There are, for example, many automotive vehicle parts for which any deterioration in impact performance due to metallizing is disfavoured.
  • In view of the aforesaid difficulty, one object of the present invention is the provision of metallized products having excellent impact properties. As a result, it has been found possible to obtain a metallized product having excellent impact properties by using, for a product which is to be metallized, a polyacetal resin composition incorporating a specific polyacrylate resin.
  • Accordingly, a polyacetal resin composition, of the invention. comprises 50 to 99.5 percent by weight of polyacetal and 0.5 to 50 percent by weight of a two or more stage polyacrylate comprising a rubber-like first stage and a thermoplastic rigid final stage.
  • The polyacrylate is preferred to be a two-stage polymer which has been obtained by polymerizing monomers such as. butyl acrylate, butylene diacrylate and allyl methacrylate or di-allyl maleate in the first stage and polymerizing methyl methacrylate in the final stage.
  • That is, one aspect of the invention provides a polyacetal composition comprising 0.5 to 50 percent by weight of a particular polyacrylate-resin based modifier incorporated into a polyacetal, and more specifically, a polyacetal resin composition wherein the polyacetal resin contains 0 to 10 percent by weight of an inorganic substance, or more particularly calcium carbonate.
  • The invention will now be described in more detail.
  • The modifier composed of a particular polyacrylate resin is advantageously a multi-stage polymer having a rubber-like first stage and a thermoplastic rigid final stage. One or more intermediate stages may be selected.
  • For example, an intermediate stage may be a polymerization of about 75 to 100 percent by weight of styrene. However, a particularly preferred polyacrylate-based modifier consists of a two-stage polymer, the first stage being a polymerization of monomers including a butyl acrylate and a butylene diacrylate as a crosslinking agent, and allyl methacrylate or diallyl maleate as a grafting agent.
  • For such a multi-stage polymer having a rubber-like first stage and a thermoplastic rigid final stage, Acryloid KM330, a product of Rohm & Haas (U.S. Pat. No. 4,096,202) can be used in the composition of the present invention. The modifier composed of such polyacrylate resin is added in a proportion of 0.5 to 50 percent by weight relative to the entire amount of the composition. If the addition is less than 0.5 percent by weight, there is no noticable improvement in the impact property, and if the addition is more than 50 percent by weight, it may be unfavourably reflected in the physical properties of the molded product. Preferably, the addition should be within the range of 3 to 15 percent by weight. If the plate adhesion of the metallized article is considered, an optimum range of addition is 5 to 15 percent by weight.
  • A polyacetal used in the composition of this invention may be a homopolymer or a copolymer. There is no particular limitation in respect of polymerization degree; the polyacetal is acceptable if it has a fair molding fluidity and if it has suitable mechanical properties for the intended product. The resin may contain other components such as a lubricant and a stabilizer. For the purpose of the invention in particular, it is preferable to use a polyacetal resin containing an inorganic substance. Among useful inorganic substances are calcium carbonate, glass, silica, talc, and pumice: more particularly, calcium carbonate is preferred. Such polyacetal resin presents a moderately rough surface after it has been subjected to pre-metallizing surface treatment, that is to say, etching, and has high activity; therefore, it exhibits very high plate adhesion. In the case of calcium carbonate being incorporated by addition into the polyacetal resin, for example, the effect of calcium carbonate on plate adhesion is satisfactory where the addition is 1 to 10 percent by weight relative to the composition as a whole: and good surface luster effect is also obtainable in that case. If the addition is more than 10 percent by weight, no stable plate adhesion can be obtained, nor is it possible to obtain a good surface effect.
  • Addition of an inorganic substance also contributes towards improving the rigidity of molded products and reducing possible dimensional change.
  • Preferably, the inorganic substance has a particle diameter, in the range of between tens of millimicrometres (mum) and say ten odd micrometres (µm); in the case of calcium carbonate, for example, heavy calcium carbonate. coke, and light calcium having a particle diameter of tens of micrometres (µm). Also various synthetics of the type having a particle diameter ranging from ten millimicrometres (mµm) to hundreds of millimicrometres (mpm). may be considered. In respect of plate adhesion, coarse particles (one micrometre (µm) to ten odd micrometres (µm)), are preferable, but if a luster effect on the metallized product is desired, fine-particle calcium carbonate is preferred, rather than heavy calcium carbonate.
  • The composition of this invention can be prepared in various ways. For example, the resin component and the modifier are melted and kneaded and then extruded into pellets by means of an extruder, which pellets are then turned out into moldings by using a molding machine. The composition of the invention can be satisfactorily metallized according to any known method.
  • Metallizing can be performed with a good plate adhesion effect by passing through such stages as degreasing, acid etching, washing, sensitizing, activation, or a combination of sensitizing and activation, such as, catalyst treatment, electroless plating, and electroplating. Preferably. etching by acid is carried out by dipping in a mixed solution of hydrochloric acid and sulfuric acid, for example. a mixed solution containing concentrated hydrochloric acid, concentrated sulfuric acid, and water in the ration of 1 : 1 : 2 by volume (about 8.6 wt % HCl + about 35.3 wt % H2SO4) for 5 to 30 minutes.
  • The invention will now be illustrated by the following examples and comparative examples: it is noted, however, that the invention is not limited by these examples.
  • To a polyacetal copolymer resin were added a polyacrylate-based modifier consisting of a multi-stage polymer having a rubber-like first stage and a thermoplastic rigid final stage (Acryloid KM330, a product of Rohm & Haas) and calcium carbonate in such ratio as shown in Table 1. The mixture was melted, kneaded, and extruded into a molding by an extruder: the molding was annealed and degreased, and then subjected to etching: subsequently, the stock was subjected to catalyst treatment and finally to metallizing. The metallized product thus obtained was tested for measurement as to Izod impact strength (notched). Also, a scar 1 cm in length, extending from the plated surface to the resin layer was given to the metallized product by using a knife, and the load required in peeling off the plate was measured for evaluation of the plate adhesion.
  • For comparison purposes, similar tests were made with a system incorporating no polyacrylate-based modifier and one incorporating a polyurethane instead of such a modifier. The test results are shown in Table 1.
    Figure imgb0001

Claims (9)

1. A polyacetal resin composition which comprises 50 to 99.5 percent by weight of polyacetal and 0.5 to 50 percent by weight of a two or more stage polyacrylate comprising a rubber-like first stage and a thermoplastic rigid final stage.
2. A polyacetal resin composition as claimed in Claim 1, in which said polyacrylate is a two-stage polymer which has been obtained by polymerizing monomers such as butyl acrylate, butylene diacrylate and allyl methacrylate or di-allyl maleate in the first stage and polymerizing methyl methacrylate in the final stage.
3. A polyacetal resin composition as claimed in Claim 1 wherein the polyacrylate is a multi-stage polymer with one or more intermediate stages included in the compostion.
4. A polyacetal resin composition as claimed in Claims 1 and 3, wherein an intermediate stage is a polymerisation of 75 to 100 percent by weight of styrene.
5. A polyacetal resin composition as claimed in Claim 1 wherein the polyacetal may be a homopolymer or a copolymer.
6. A polyacetal resin composition as claimed in Claim 1 or 2, which further comprises an inorganic substance.
7. A polyacetal resin composition as claimed in Claim 1 or 2, which further comprises 1 to 10 percent by weight relative to the composition as a whole of calcium carbonate.
8. A polyacetal resin composition as claimed in Claim 1 which further comprises one or more of any known lubricant, stabilizer or filler means.
9. A polyacetal resin composition according to claim 1,and substantially as described with reference to any one of the foregoing Examples 1 to 6.
EP86300552A 1985-02-04 1986-01-28 Polyacetal resin composition Ceased EP0192356A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60019766A JPH0665704B2 (en) 1985-02-04 1985-02-04 Polyacetal resin composition for plating
JP19766/85 1985-02-04

Publications (2)

Publication Number Publication Date
EP0192356A2 true EP0192356A2 (en) 1986-08-27
EP0192356A3 EP0192356A3 (en) 1988-01-13

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EP86300552A Ceased EP0192356A3 (en) 1985-02-04 1986-01-28 Polyacetal resin composition

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US (1) US4886851A (en)
EP (1) EP0192356A3 (en)
JP (1) JPH0665704B2 (en)
CA (1) CA1266141A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0300573A1 (en) * 1987-07-15 1989-01-25 Asahi Kasei Kogyo Kabushiki Kaisha Molded article comprising a weather-resistant polyoxymethylene composition
EP0356167A2 (en) * 1988-08-22 1990-02-28 Polyplastics Co. Ltd. Weather-resistant polyacetal resin composition
EP0386597A2 (en) * 1989-03-04 1990-09-12 Röhm Gmbh Plastics compositions
EP0480314A2 (en) * 1990-10-08 1992-04-15 Degussa Ag Polyoxymethylene moulding compositions having an increased thermal stability and a reduced emission of formaldehyde
EP0494534A2 (en) * 1990-12-28 1992-07-15 Polyplastics Co. Ltd. Core-shell polymer
EP0519749A2 (en) * 1991-06-20 1992-12-23 Polyplastics Co. Ltd. Weather-resistant polyacetal resin composition
EP0558279A1 (en) * 1992-02-26 1993-09-01 Asahi Kasei Kogyo Kabushiki Kaisha An acetal resin composition
US5294661A (en) * 1987-07-15 1994-03-15 Asahi Kasei Kogyo Kabushiki Kaisha Weather-resistant polyoxymethylene composition and molded article thereof
WO2004058886A1 (en) * 2002-12-17 2004-07-15 E.I. Du Pont De Nemours And Company Compatibility improvement in crystalline thermoplastics with mineral fillers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100869619B1 (en) * 2001-12-21 2008-11-21 미츠비시 가스 가가쿠 가부시키가이샤 Thermoplastic resin composition
US6974849B2 (en) * 2003-03-03 2005-12-13 Ticona Llc Polyacetals with improved resistance to bleach
US9550845B2 (en) 2014-04-08 2017-01-24 The Board Of Trustees Of The University Of Illinois Multiple stage curable polymer with controlled transitions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1964156A1 (en) * 1969-12-22 1971-06-24 Basf Ag Thermoplastic molding compounds with high impact strength
FR2439803A1 (en) * 1978-10-25 1980-05-23 Asahi Chemical Ind POLYACETAL RESIN COMPOSITION EXCELLENT IN ITS HEAT STABILITY AND EASY PROCESSING, PROCESS FOR MAKING ITS SURFACE ROUGH AND PRODUCT OBTAINED
EP0115373A2 (en) * 1983-01-04 1984-08-08 Celanese Corporation Polyacetal moulding compositions with high impact resistance

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3027352A (en) * 1958-02-28 1962-03-27 Celanese Corp Copolymers
US4096202A (en) * 1976-06-09 1978-06-20 Rohm And Haas Company Impact modified poly(alkylene terephthalates)
US4296216A (en) * 1980-03-05 1981-10-20 Sumitomo Naugatuck Co., Ltd. Thermoplastic resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1964156A1 (en) * 1969-12-22 1971-06-24 Basf Ag Thermoplastic molding compounds with high impact strength
FR2439803A1 (en) * 1978-10-25 1980-05-23 Asahi Chemical Ind POLYACETAL RESIN COMPOSITION EXCELLENT IN ITS HEAT STABILITY AND EASY PROCESSING, PROCESS FOR MAKING ITS SURFACE ROUGH AND PRODUCT OBTAINED
EP0115373A2 (en) * 1983-01-04 1984-08-08 Celanese Corporation Polyacetal moulding compositions with high impact resistance

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5294661A (en) * 1987-07-15 1994-03-15 Asahi Kasei Kogyo Kabushiki Kaisha Weather-resistant polyoxymethylene composition and molded article thereof
EP0300573A1 (en) * 1987-07-15 1989-01-25 Asahi Kasei Kogyo Kabushiki Kaisha Molded article comprising a weather-resistant polyoxymethylene composition
USRE34141E (en) * 1988-08-22 1992-12-08 Polyplastics Co., Ltd. Weather-resistant polyacetal resin composition and molded articles therefrom
EP0356167A2 (en) * 1988-08-22 1990-02-28 Polyplastics Co. Ltd. Weather-resistant polyacetal resin composition
EP0356167A3 (en) * 1988-08-22 1991-05-29 Polyplastics Co. Ltd. Weather-resistant polyacetal resin composition
EP0386597A2 (en) * 1989-03-04 1990-09-12 Röhm Gmbh Plastics compositions
EP0386597A3 (en) * 1989-03-04 1991-07-31 Röhm Gmbh Plastics compositions
US5212237A (en) * 1989-03-04 1993-05-18 Roehm Gmbh Polymer mixtures
EP0480314A3 (en) * 1990-10-08 1993-01-07 Degussa Ag Polyoxymethylene moulding compositions having an increased thermal stability and a reduced emission of formaldehyde
US5218041A (en) * 1990-10-08 1993-06-08 Degussa Aktiengesellschaft Polyoxymethylene molding materials having improved thermal stability and reduced formaldehyde emission
EP0480314A2 (en) * 1990-10-08 1992-04-15 Degussa Ag Polyoxymethylene moulding compositions having an increased thermal stability and a reduced emission of formaldehyde
EP0494534A3 (en) * 1990-12-28 1992-08-12 Polyplastics Co. Ltd. Core-shell polymer
EP0494534A2 (en) * 1990-12-28 1992-07-15 Polyplastics Co. Ltd. Core-shell polymer
US5484845A (en) * 1990-12-28 1996-01-16 Polyplastics Co., Ltd. Polyacetal compositions having surface gloss reducing effective amounts of core-shell polymers
EP0519749A2 (en) * 1991-06-20 1992-12-23 Polyplastics Co. Ltd. Weather-resistant polyacetal resin composition
EP0519749A3 (en) * 1991-06-20 1993-03-03 Polyplastics Co. Ltd. Weather-resistant polyacetal resin composition
US5258431A (en) * 1991-06-20 1993-11-02 Polyplastics Co., Ltd. Weather-resistant polyacetal resin compositions exhibiting reduced surface gloss characteristics, and molded articles thereof
EP0558279A1 (en) * 1992-02-26 1993-09-01 Asahi Kasei Kogyo Kabushiki Kaisha An acetal resin composition
US5354810A (en) * 1992-02-26 1994-10-11 Asahi Kasei Kogyo Kabushiki Kaisha Acetal resin composition
WO2004058886A1 (en) * 2002-12-17 2004-07-15 E.I. Du Pont De Nemours And Company Compatibility improvement in crystalline thermoplastics with mineral fillers
US6936651B2 (en) 2002-12-17 2005-08-30 E. I. Du Pont De Nemours And Company Compatibility improvement in crystalline thermoplastics with mineral fillers

Also Published As

Publication number Publication date
US4886851A (en) 1989-12-12
JPH0665704B2 (en) 1994-08-24
CA1266141A (en) 1990-02-20
EP0192356A3 (en) 1988-01-13
JPS61179254A (en) 1986-08-11

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